This invention relates to novel color developing agent precursors, a dye-forming method, color developing compositions and photosensitive materials. More particularly, it relates to color developing agent precursors, a dye-forming method, color developing compositions and photosensitive materials which are useful in, for example, color printing materials for outputting digital image data.
There have been widely employed photosensitive materials for obtaining images by forming dyes via coupling reactions. For example, conventional silver halide color photosensitive materials fall within this category of photosensitive materials for forming images with the use of coupling reactions. As an example of the methods for forming images on silver halide photosensitive materials, citation may be made of a method which involves the steps of incorporating a color developing agent and a colorless coupler into a material, oxidizing the color developing agent by using a silver halide in accordance with image data and coupling the obtained oxidant with the colorless coupler, thereby forming an image.
In the conventional silver halide photographic photosensitive materials, silver halides which oxidize color developing agents are needed in the formation of dyes. Silver halides, which oxidize relatively stable color developing agents contained in materials, are extremely strong oxidizing agents. Thus, it becomes difficult in some cases to contain such silver halides in a stable state together with couplers and surrounding media in materials. In addition, silver halides are expensive, which causes an increase in the production cost of silver halide photographic light-sensitive materials. Furthermore, the conventional image-forming method with the use of silver halide photographic light-sensitive materials usually involve complicated steps of development by using processing liquids, bleaching and fixing. Therefore, it is advantageous in view of cost and operation to employ a photosensitive material on which an image can be more conveniently formed without resort to any oxidizing agents. In recent years, there arises a strong demand for an image-forming method whereby full color digital image data can be economically and easily output. Therefore, it is profitable, if possible, to economically and easily form an image without using silver halides.
An object of the invention is to provide a method whereby a dye can be economically and easily formed without resort to any oxidizing agents such as silver halides; color developing compositions; and photosensitive materials using the same. Another object of the invention is to provide image-forming materials (in particular, image-forming materials for digital image data output) on which an image can be easily and economically formed without a need for liquid processing; and an image-forming method.
Other objects and effects of the present invention will become apparent from the following description.
The above-described objects of the present invention have been achieved by providing the following means.
(1) A dye-forming method comprising:
reacting a dye-forming coupler and a color developing agent precursor represented by the following general formula (I): 
wherein A3 represents a group other than a hydrogen atom which leaves, accompanied by the bonding electron pair with the nitrogen atom in general formula (I), to thereby form a color developing agent; A2 represents a group which leaves in association with a dye-formation; and A1 represents a group which forms a dye together with the nitrogen atom and the coupler.
(2) The dye-forming method according to the above (1), wherein said color developing agent precursor represented by general formula (I) is a compound represented by the following general formula (II): 
wherein Z represents xe2x80x94OH, xe2x80x94OPG or xe2x80x94NR1R2 (wherein PG represents a protective group; and R1 and R2 represent each an alkyl group or an aryl group); R3, R4, R5 and R6 represent each a hydrogen atom or a substituent; A3represents a group which leaves from the nitrogen atom in general formula (II) accompanied by a bonding electron pair; and A2 represents a group which leaves in association with the dye-formation; or R1, R2, R3, R4, R5 and R6 may be bonded to each other to form a ring in case of being possible.
(3) The dye-forming method according to the above (1), wherein the color developing agent precursor represented by general formula (I) is a compound represented by the following general formula (III): 
wherein A4 represents a substituent; n is an integer of 0 to 4; A5, A6 and A7 represent each a hydrogen atom or a substituent; A8 represents a group represented by xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94N(A11)xe2x80x94 or xe2x80x94C(A12) (A13)xe2x80x94 (wherein A11 to A13 represents each a substituent); A9 represents a group represented by xe2x95x90O, xe2x95x90S, xe2x95x90Nxe2x80x94A14 or xe2x95x90C(A15)xe2x80x94C(A16)xe2x95x90Nxe2x80x94A17 (wherein A14 to A17 represents each a substituent); and A10 represents a substituent.
(4) The dye-forming method according to the above (1), wherein group A2 is a group which leaves in association with the dye-formation after the formation of a dye precursor via coupling between the color developing agent, which has been formed by the elimination of A3, and the dye-forming coupler.
(5) The dye-forming method according to the above (2), wherein group A2 is a group which leaves in association with the dye-formation after the formation of a dye precursor via coupling between the color developing agent, which has been formed by the elimination of A3, and the dye-forming coupler.
(6) The dye-forming method according to the above (3), wherein group A2 is a group which leaves in association with the dye-formation after the formation of a dye precursor via coupling between the color developing agent, which has been formed by the elimination of A3, and the dye-forming coupler.
(7) The dye-forming method according to the above (1), wherein an activator or a precursor thereof, which is capable of acting on group A3 in general formula (I) to thereby form a color developing agent, is further used.
(8) The dye-forming method according to the above (7), wherein said general formula (I) is represented by the following general formula (II): 
wherein Z represents xe2x80x94OH, xe2x80x94OPG or xe2x80x94NR1R2 (wherein PG represents a protective group; and R1, and R2 represent each an alkyl group or an aryl group); R3, R4, R5 and R6 represent each a hydrogen atom or a substituent; A3 represents a group which leaves from the nitrogen atom in general formula (II) accompanied by a bonding electron pair; and A2 represents a group which leaves in association with the dye-formation; or R1, R2, R3, R4, R5 and R6 may be bonded to each other to form a ring in case of being possible.
(9) The dye-forming method according to the above (7), wherein said general formula (I) is represented by the following general formula (III): 
wherein A4 represents a substituent; n is an integer of 0 to 4; A5, A6 and A7 represent each a hydrogen atom or a substituent; A8 represents a group represented by xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94N(A11)xe2x80x94 or xe2x80x94C(A12) (A13)xe2x80x94 (wherein A11 to A13 represents each a substituent); A9 represents a group represented by xe2x95x90O, xe2x95x90S, xe2x95x90Nxe2x80x94A14 or xe2x95x90C(A15)xe2x80x94C(A16)xe2x95x90Nxe2x80x94A17 (wherein A14 to A17 represents each a substituent); and A10 represents a substituent.
(10) The dye-forming method according to the above (7), wherein the activation effect of said activator is based on a nucleophilic substitution reaction or a nucleophilic addition reaction of A3 with respect to an atom in the activator.
(11) The dye-forming method according to the above (7), wherein said activator contains a metal atom.
(12) A dye-forming method comprising forming a dye by reacting:
a precursor of an oxidation product of a p-phenylenediamine derivative or a p-aminophenol derivative;
an activator containing a metal atom which is capable of reacting with said precursor to thereby form an oxidation product of the p-phenylenediamine derivative or the p-aminophenol derivative; and
a dye-forming coupler capable of undergoing a coupling reaction with said oxidant of the p-phenylenediamine derivative or the p-aminophenol derivative to thereby form a dye.
(13) A dye-forming method comprising forming a dye by reacting:
1) a color developing agent precursor represented by general formula (Ia): 
wherein Z represents a hydroxyl group or xe2x80x94NR1R2 (wherein R1 and R2 represent each an alkyl group or an aryl group); R3, R4, R5 and R6 represent each a hydrogen atom or a substituent; AGa represents a group which enables the compound of general formula (Ia) to interact with the compound of general formula (Q); L represents a group which leaves, as the result of said interaction, from the nitrogen atom in the compound of general formula (Ia) accompanied by the bonding electron pair; BG represents a blocking group which leaves in the course of the dye-formation; and R1, R2, R3, R4, R5, and R6 may be bonded to each other to form a ring in case of being possible;
2) an activator represented by general formula (Q): 
wherein M represents a metal atom having an electric charge n (wherein n is an integer of from 0 to 7); Aa represents an atomic group which neutralizes the electric charge of said metal ion; and m is an integer of from 0 to 7, provided that when n is 0, it is unnecessary that Aa neutralizes the electric charge of M and m is an integer of from 0 to 6, and when m is 2 or more, plurality of Aa may be either the same or different and may form a bonded structure together; and
3) a dye-forming coupler capable of reacting with an activated color developing agent, which is formed by the reaction between the compound represented by general formula (Ia) and the compound represented by general formula (Q) to thereby form a dye.
(14) The dye-forming method according to the above (11), wherein said metal atom is a copper, zinc or silver atom.
(15) The dye-forming method according to the above (7), wherein said activator contains a metal cation, and at least one compound selected from the group consisting of a halide anion, a carboxylic acid anion, a sulfonic acid anion, a sulfuric acidmonoester anion, a phosphoric acid diester anion, a xcex2-ketoester anion, a xcex2-diketone anion, an oxime anion, a hydroxamic acid anion, a tetraphenylboric acid anion, a phosphorus hexafluoride anion and a boron tetrafluoride anion.
(16) The dye-forming method according to the above (7), wherein said activator contains a meso-ion complex of a metal salt.
(17) The dye-forming method according to the above (16), wherein said meso-ion complex of a metal salt is a compound represented by the following general formula (IV):
(Mn+)p(A)q(B)rxe2x80x83xe2x80x83(IV)
wherein M represents a metal atom having a positive electric charge n; n is an integer of from 0 to 7; p is an integer of from 1 to 24; A represents an atomic group which has a negative electric charge of 1 to 7 and neutralizes the charge of the metal atom; q is an integer of from 0 to 24, provided that when q is 2 or more, plurality of A may be either the same or different and may form a bonded structure together; B represents an atomic group represented by general formula (V); r is an integer of from 1 to 24, provided that when r is 2 or more, plurality of B may be either the same or different and may form a bonded structure together; and the compound of formula (IV) may optionally have another atomic group bonded thereto which does not substantially neutralize the electric charges of other group: 
wherein Y represents O, S or Nxe2x80x94R9; R7 and R9 represent each a substituent; and R8 represents a hydrogen atom or a substituent.
(18) The dye-forming method according to the above (17), wherein Y in general formula (V) represents Nxe2x80x94R9; R7 and R9 represent each an alkyl group, an aryl group or a heterocyclic group; and R8 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.
(19) The dye-forming method according to the above (16), wherein said color developing agent precursor is at least one member selected from p-phenylenediamine derivatives and p-aminophenol derivatives.
(20) The dye-forming method according to the above (16), wherein said color developing agent precursor is a compound represented by the following general formula (Ib): 
wherein Z represents xe2x80x94OH, xe2x80x94O(PG) or xe2x80x94NR1R2 (wherein PG represents a protective group; and R1 and R2 represent each an alkyl group or an aryl group); R3, R4, R5 and R6 represent each a hydrogen atom or a substituent; AGb represents a group which is capable of undergoing interaction with a meso-ion complex of a metal salt; L represents a group which leaves, as the result of said interaction, from the nitrogen atom in the compound of general formula (Ib) accompanied by the bonding electron pair; and BG represents a blocking group which leaves in the course of the dye-formation; or R1, R2, R3, R4, R5 and R6 may be bonded to each other to form a ring in case of being possible.
(21) A photosensitive material which contains:
a color developing agent precursor represented by general formula (I): 
wherein A3 represents a group other than a hydrogen atom which leaves, accompanied by the bonding electron pair with the nitrogen atom in general formula (I), to thereby form a color developing agent; A2 represents a group which leaves in association with a dye-formation; and Al represents a group which forms a dye together with the nitrogen atom and the coupler;
a dye-forming coupler;
an activator capable of acting on group A3 in general formula (I) to thereby form a color developing agent;
a polymerizable compound; and
a photopolymerization initiator,
provided that said polymerizable compound may be the same molecule as said color developing agent precursor, dye-forming coupler or activator.
(22) The photosensitive material according to the above (21), wherein general formula (I) is represented by general formula (II): 
wherein Z represents xe2x80x94OH, xe2x80x94OPG or xe2x80x94NR1R2 (wherein PG represents a protective group; and R1 and R2 represent each an alkyl group or an aryl group); R3, R4, R5, and R6 represent each a hydrogen atom or a substituent; A3 represents a group which leaves from the nitrogen atom in general formula (II) accompanied by a bonding electron pair; and A2 represents a group which leaves in association with the dye-formation; or R1, R2, R3, R4, R5 and R6 may be bonded to each other to form a ring in case of being possible.
(23) The photosensitive material according to the above (21), wherein general formula (I) is represented by general formula (III): 
wherein A4 represents a substituent; n is an integer of 0 to 4; A5, A6 and A7 represent each a hydrogen atom or a substituent; A8 represents a group represented by xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94N(A11)xe2x80x94 or xe2x80x94C (A12) (A13)xe2x80x94 (wherein A11 to A13 represents each a substituent); A9 represents a group represented by xe2x95x90O, xe2x95x90S, xe2x95x90Nxe2x80x94A14 or xe2x95x90C(A15)xe2x80x94C(A16)xe2x95x90Nxe2x80x94A17 (wherein A14 to A17 represents each a substituent); and A10 represents a substituent.
(24) The photosensitive material according to the above (21), wherein the activation effect of said activator is based on a nucleophilic substitution reaction or a nucleophilic addition reaction of A3with respect to an atom in the activator.
(25) The photosensitive material according to the above (21), wherein said activator contains a metal atom.
(26) A photosensitive material which contains:
a precursor of an oxidation product of a p-phenylenediamine derivative or a p-aminophenol derivative, as a color developing agent precursor;
an activator containing a metal atom which is capable of reacting with said color developing agent precursor to thereby form the oxidation product of the p-phenylenediamine derivative or the p-aminophenol derivative;
a dye-forming coupler capable of undergoing a coupling reaction with said oxidation product of the p-phenylenediamine derivative or the p-aminophenol derivative to thereby form a dye;
a polymerizable monomer; and
a photopolymerization initiator,
provided that said polymerizable monomer may be the same molecule as said color developing agent precursor, activator or dye-forming coupler.
(27) A photosensitive material which contains:
a color developing agent precursor represented by general formula (Ia): 
wherein Z represents a hydroxyl group or xe2x80x94NR1R2 (wherein R1 and R2 represent each an alkyl group or an aryl group); R3, R4, R5 and R6 represent each a hydrogen atom or a substituent; AGa represents a group which enables the compound of general formula (Ia) to interact with the compound of general formula (Q); L represents a group which leaves, as the result of said interaction, from the nitrogen atom in the compound of general formula (Ia) accompanied by the bonding electron pair; BG represents a blocking group which leaves in the course of the dye-formation; and R1, R2, R3, R4, R5 and R6 may be bonded to each other to form a ring in case of being possible;
an activator represented by general formula (Q): 
wherein M represents a metal atom having an electric charge n (wherein n is an integer of from 0 to 7); Aa represents an atomic group which neutralizes the electric charge of said metal ion; and m is an integer of from 0 to 7, provided that when n is 0, it is unnecessary that Aa neutralizes the electric charge of M and m is an integer of from 0 to 6, and when m is 2 or more, plurality of Aa may be either the same or different and may form a bonded structure together;
a dye-forming coupler capable of reacting with an activated color developing agent, which is formed by the reaction between the compound represented by general formula (Ia) with the compound represented by general formula (Q) to thereby form a dye;
a polymerizable monomer; and
a photopolymerization initiator,
provided that said polymerizable monomer may be the same molecule as said color developing agent precursor, activator or dye-forming coupler.
(28) The photosensitive material according to the above (25), wherein said metal atom is a copper, zinc or silver atom.
(29) The photosensitive material according to the above (21), wherein said activator contains a metal cation, and at least one compound selected from the group consisting of a halide anion, a carboxylic acid anion, a sulfonic acid anion, a sulfuric acid monoester anion, a phosphoric acid diester anion, a xcex2-ketoester anion, a xcex2-diketone anion, an oxime anion, a hydroxamic acid anion, a tetraphenylboric acid anion, a phosphorus hexafluoride anion and a boron tetrafluoride anion.
(30) The photosensitive material according to the above (21), wherein said activator contains a meso-ion complex of a metal salt.
(31) The photosensitive material according to the above (30), wherein said meso-ion complex of a metal salt is a compound represented by the following general formula (IV):
(Mn+)p(A)q(B)rxe2x80x83xe2x80x83(IV)
wherein M represents a metal atom having a positive electric charge n; n is an integer of from 0 to 7; p is an integer of from 1 to 24; A represents an atomic group which has a negative electric charge of 1 to 7 and neutralizes the charge of the metal atom; q is an integer of from 0 to 24, provided that when q is 2 or more, plurality of A may be either the same or different and may form a bonded structure together; B represents an atomic group represented by general formula (V); r is an integer of from 1 to 24, provided that when r is 2 or more, plurality of B may be either the same or different and may form a bonded structure together; and the compound of formula (IV) may optionally have another atomic group bonded thereto which does not substantially neutralize the electric charges of other group: 
wherein Y represents O, S or Nxe2x80x94R9; R7 and R9 represent each a substituent; and R8 represents a hydrogen atom or a substituent.
(32) The photosensitive material according to the above (31), wherein Y in general formula (V) represents Nxe2x80x94R9; R7 and R9 represent each an alkyl group, an aryl group or a heterocyclic group; and R8 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.
(33) A compound represented by the following general formula (VI): 
wherein A21 and A24 represent each a substituent; n is an integer of from 0 to 4; A22 and A23 represent each an alkyl group; and A25 represents xe2x80x94C (xe2x95x90O)xe2x80x94A26 or xe2x80x94SO2xe2x80x94A27 (wherein A26 and A27 represent each a substituent).
(34) The compound according to the above (33), wherein A24 is represented by general formula (VII) and A25 is represented by general formula (VIII): 
wherein A28 represents xe2x95x90O, xe2x95x90S or xe2x95x90Nxe2x80x94A31 (wherein A31 represents a substituent); and A29 and A30 represent each a hydrogen atom or a substituent.
(35) A color developing composition which contains a color developing agent precursor represented by general formula (I) and a dye-forming coupler.
(36) The color developing composition according to the above (35), wherein the color developing agent precursor represented by general formula (I) is a compound represented by general formula (II).
(37) The color developing composition according to the above (35), wherein the color developing agent precursor represented by general formula (I) is a compound represented by general formula (III).
Examples of the color developing agent precursor of the invention include compounds prepared by capturing oxidants of color developing agents, which are usable in silver halide photographic photosensitive materials, by chemical species other than couplers (hereinafter, these chemical species will be called xe2x80x9ccapturersxe2x80x9d). In this case, the capturer moiety in the color developing agent precursor is activated in the course of the dye-formation and an interchange between the capturer and the coupler takes place, thereby forming a dye.
It is favorable that the color developing agent precursor, which is particularly represented by general formula (I), is at least one member selected from among p-phenylenediamine derivatives and p-aminophenol derivatives. It is favorable that the p-phenylenediamine derivative or the p-aminophenol derivative is a compound having a moiety which is activated by an activator and leaves to thereby convert the derivative into an oxidant.
Preferable examples of the color developing agent precursor are compounds represented by the following general formula (II). 
In general formula (II), Z represents xe2x80x94OH, xe2x80x94O(PG) or xe2x80x94NR1R2 wherein PG represents a protective group. As this protective group, use may be made of common ones.
R1 and R2 represent each an alkyl group or an aryl group or R1 and R2 may be bonded to each other to form a heterocyclic group. The alkyl groups represented by R1 and R2 include both of substituted alkyl groups and unsubstituted alkyl groups. These alkyl groups may be either branched or linear. When R1 and R2 represent each a substituted alkyl group, examples of the substituent include a cyano group, a sulfonylamino group, an acyl group, a hydroxyl group, an acylamino group, an acyloxy group, halogen atoms and alkyloxycarbonyl groups. These substituents may be further substituted by, for example, an alkyl group or an aryl group. Particular examples of the alkyl groups include methyl group, ethyl group, propyl group, dodoecyl group, 2-hydroxyethyl group,2-cyanoethyl group, cyanomethyl group, 2-methoxyethyl group, 2-ethoxycarbonyl group and 2-(methylsulfonylamino)ethyl group.
The aryl groups represented by R1 and R2, include both of substituted aryl groups and unsubstituted aryl groups. These aryl groups may have either a monocyclic structure or a fused ring structure composed of two or more rings fused together. When R1, and R2, represent each a substituted aryl group, examples of the substituent include those which will be cited hereinafter as examples of substituents represented by R3 to R6. These substituents may be further substituted by, for example, an alkyl group or an aryl group. Particular examples of the aryl groups include phenyl group and naphthyl group.
Alternatively, R1 and R2 may be bonded together to form a heterocyclic group. The heterocyclic group may be either a substituted group or an unsubstituted group. As the heterocyclic group, 5-, 6- or 7-membered heterocyclic group is favorable. The heterocyclic groups may have either a monocyclic structure or a fused ring structure composed of two or more rings fused together. As the hetero atom involved in the heterocyclic group, a nitrogen atom, an oxygen atom or a sulfur atom is favorable.
In general formula (I) as given above, R3, R4, R5, and R6 represent each a hydrogen atom or a substituent.
Preferable examples of the substituents represented respectively by R3, R4, R5 and R6 include halogen atoms (for example, chloro, bromo), alkyl groups (for example, methyl, ethyl, isopropyl, n-butyl, t-butyl), aryl groups (for example, phenyl, tolyl, xylyl), heterocyclic groups (for example, 2-pyridyl, N-pyrrolidinyl), carbonamido groups (for example, acetylamino, propionylamino, butyroylamino, benzoylamino), sulfonamido groups (for example, methanosulfonylamino, ethanesulfonylamino, benzenesulfonylamino, toluenesulfonylamino), alkoxy groups (for example, methoxy, ethoxy), aryloxy groups (for example, phenoxy), alkylthio groups (for example, methylthio, ethylthio, butylthio), arylthio groups (for example, phenylthio, tolylthio), amino groups (for example, methylamino, phenylamino), carbamoyl groups (for example, methylcarbamoyl, dimethylcarbamoyl, ethylcarbamoyl, diethylcarbamoyl, dibutylcarbamoyl, piperidinocarbamoyl, morpholinocarbamoyl, phenylcarbamoyl, methylphenylcarbamoyl, ethylphenylcarbamoyl, benzylphenylcarbamoyl), sulfamoyl groups (for example, methylsulfamoyl, dimethylsulfamoyl, ethylsulfamoyl, diethylsulfamoyl, dibutylsulfamoyl, piperidinosulfamoyl, morpholinosulfamoyl, phenylsulfamoyl, mehtylphenylsulfamoyl, ethylphenylsulfamoyl, benzylphenylsulfamoyl), cyano group, sulfonyl groups (for example, methanesulfonyl, ethanesulfonyl, phenylsulfonyl, 4-chlorophenylsulfonyl, p-toluenesulfonyl), alkoxycarbonyl groups (for example, methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl), aryloxycarbonyl groups (for example, phenoxycarbonyl), acyl groups (for example, acetyl, propionyl, butyroyl, benzoyl, alkylbenzoyl), ureido groups (for example, methylaminocarbonamido, diethylaminocarbonamido), urethane groups (for example, methoxycarbonamido, butoxycarbonamido) and acyloxy groups (for example, acetyloxy, propionyloxy, butyroyloxy).
R1 and R3, R1 and R5, R2 and R3, and R2 and R5 may be each bonded together to form a heterocycle, preferably a 5- to 7-membered heterocycle. It is also possible that R3 and R4, and R5 and R3 are each bonded together to form a ring. In this case, the rings may be either heterocycles or homocylces. Moreover, each of these cycles may be saturated, partly saturated or incompletely saturated and preferably have from 5 to 7 members.
A3 represents a moiety corresponding to the capturer as described above. Namely, A3 represents a group which leaves under the action of heat or an activator. In case of leaving under the action of an activator, A3 has an atomic group capable of undergoing interaction with the activator. Examples of the atomic group capable of undergoing the interaction with an activator include carboxyl groups, thiocarbonyl groups, selenocarbonyl groups, tellurocarbonyl groups, thioether groups, selenoether groups, amino groups, ether groups, hydroxy groups (including enol, phenol), carboamido groups, polyether groups, crown ether groups, azo groups, hydroxyimino groups, imino groups, carbonyl groups and heterocyclic groups having a nitrogen atom or a sulfur atom in the ring. Among all, carboxyl groups, thiocarbonyl groups, thioether groups, amino groups, hydroxy groups (including enol, phenol), polyether groups, crown ether groups, hydroxyimino groups, imino groups and heterocyclic groups having a nitrogen atom or a sulfur atom in the ring are preferable and carboxyl groups, thiocarbonyl groups, amino groups, hydroxyimino groups and heterocyclic groups having a nitrogen atom or a sulfur atom in the ring are still preferable. It is also preferable to use atomic groups composed of these groups combined together.
Preferable examples of A3 are groups having a partial structure represented by the following general formula (IX). 
In general formula (IX), xe2x80x9c★xe2x80x9d stands for a moiety bonded to the nitrogen atom.
In general formula (IX), X represents a sulfur atom, a selenium atom, an xe2x95x90NOH group or an xe2x95x90NR11 group.
In general formula (IX), Y represents a sulfur atom, an oxygen atom, xe2x80x94N(R12)xe2x80x94 or xe2x80x94C(R13) (R14)xe2x80x94. It is preferable that Y is a sulfur atom, an oxygen atom or xe2x80x94N(R12)xe2x80x94.
In general formula (IX), R10 represents an alkyl group, an aryl group or a heterocyclic group, and R11, R12, R13 and R14 represent each an alkyl group, an aryl group or a heterocyclic group. Examples of these alkyl and aryl groups include those cited above as examples of the groups represented by R3 to R6. Examples of the heterocyclic groups include those cited above as examples of the groups formed by bonding R1 and R3 to each other. R10 and R11, R10 and R12, R10 and R13, R10 and R14 and R13 and R14 may be each bonded together to form a ring, preferably a 5- to 7-membered ring.
In general formula (IX), L represents a group which leaves, as the result of heating or interaction with an activator, from the nitrogen atom in general formula (I) accompanied with a bonding electron pair. It is preferable that Lisa sulfur atom, xe2x80x94N(R15)xe2x80x94 or xe2x80x94C(R16) (R17)xe2x80x94. R15 represents an alkyl group, an aryl group, a heterocyclic group or a bond. Examples of these alkyl and aryl groups include those cited above as examples of the groups represented by R3 to R6. Examples of the heterocyclic groups include those cited above as examples of the groups formed by bonding R1 and R3 to each other. At least one of R15, R16 and R17 may be bonded to xe2x80x94C(xe2x95x90X)xe2x80x94Yxe2x80x94R10 to form a ring, which is preferably a 5- to 7-membered ring. R16 and R17 represent each an alkyl group, an aryl group, a heterocyclic group, a cyano group, a trifluoromethyl group, a sulfonyl group, a carbamoyl group, a halogen atom, an amido group, a sulfamoyl group, an acyl group or a bond. Examples of these groups include those cited above as examples of the groups represented by R3 to R6. Examples of the heterocyclic groups include those cited above as examples of the groups formed by bonding R1 and R3 to each other. R16 and R17, R18 and xe2x80x94C (xe2x95x90X)xe2x80x94Yxe2x80x94R10, and R17 and xe2x80x94C (xe2x95x90X) xe2x80x94Yxe2x80x94R10 may be each bonded together to form a ring, which is preferably a 5- to 7-membered ring. It is favorable that at least one of R16 and R17 is a group having a Hammett sigma-para (xcex4p) constant of +0.3 or more (for example, cyano, trifluoromethyl, sulfonyl, carbamoyl, sulfamoyl, acyl).
In general formula (II), A2 represents a protective group which leaves in the course of the dye-formation. It is preferable that A2 also has a function of stabilizing the compound represented by general formula (II). From this viewpoint, an electrophilic group is preferable therefor. Among all, it is preferable that A2 is a group represented by the following general formula (X).
★★xe2x80x94Wxe2x80x94R18xe2x80x83xe2x80x83(X)
In general formula (X), xe2x80x9c★★xe2x80x9d represents a moiety bonded to the nitrogen atom in general formula (II).
In general formula (X), W represents an electrophilic divalent group. It is particularly preferable that W represents xe2x80x94SO2xe2x80x94, xe2x80x94CON(R19)xe2x80x94, xe2x80x94COOxe2x80x94 or xe2x80x94SO2N(R19)xe2x80x94 and xe2x80x94CON(R19)xe2x80x94 is the most desirable. R19 represents a hydrogen atom, an alkyl group or an aryl group. Among all, it is preferable that R19 is a hydrogen atom.
In general formula (X), R18 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group or an alkoxy group. Among all, it is preferable that R18 represents an alkyl group or an aryl group and an alkyl group is the most desirable. Examples of these alkyl and aryl groups include those cited above as examples of the groups represented by R3 to R6.
In general formulae (Ia) and (Ib), R4 to R6 are as defined in general formula (II). L-AGa and L-AGb correspond to A3 in general formula (II) while BG corresponds to A2 in general formula (II) and examples thereof are also the same as described with respect to A3 and A2.
Examples of A4 in general formula (III) include halogen atoms (for example, chloro, bromo), alkyl groups (for example, methyl, ethyl, isopropyl, n-butyl, t-butyl), aryl groups (for example, phenyl, tolyl, xylyl), heterocyclic groups (for example, 2-pyridyl, N-pyrrolidinyl), carbonamido groups (for example, acetylamino, propionylamino, butyroylamino, benzoylamino), sulfonamido groups (for example, methanosulfonylamino, ethanesulfonylamino, benzenesulfonylamino, toluenesulfonylamino), alkoxy groups (for example, methoxy, ethoxy), aryloxy groups (for example, phenoxy), alkylthio groups (for example, methylthio, ethylthio, butylthio), arylthio groups (for example, phenylthio, tolylthio), amino groups (for example, unsubstituted amino, amino substituted by aliphatic or aromatic groups such as methylamino, phenylamino), carbamoyl groups (for example, carbamoyl substituted by aliphatic, aromatic or heterocyclic groups and carbamoyl having a ring formed by the linkage of nitrogen atoms, such as methylcarbamoyl, dimethylcarbamoyl, ethylcarbamoyl, diethylcarbamoyl, dibutylcarbamoyl, piperidinocarbamoyl, morpholinocarbamoyl, phenylcarbamoyl, methylphenylcarbamoyl, ethylphenylcarbamoyl, benzylphenylcarbamoyl), sulfamoyl groups (for example, sulfamoyl substituted by aliphatic, aromatic or heterocyclic groups-and sulfamoyl having a ring formed by the linkage of nitrogen atoms, such as methylsulfamoyl, dimehtylsulfamoyl, ethylsulfamoyl, diethylsulfamoyl, dibutylsulfamoyl, piperidinosulfamoyl, morpholinosulfamoyl, phenylsulfamoyl, mehtylphenylsulfamoyl, ethylphenylsulfamoyl, benzylphenylsulfamoyl), cyano group, sulfonyl groups (for example, methanesulfonyl, ethanesulfonyl, phenylsulfonyl, 4-chlorophenylsulfonyl, p-toluenesulfonyl), alkoxycarbonyl groups (for example, methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl), aryloxycarbonyl groups (for example, phenoxycarbonyl), acyl groups (for example, acetyl, propionyl, butyroyl, benzoyl, alkylbenzoyl), ureido groups (for example, methylaminocarbonamido, diethylaminocarbonamido), urethane groups (for example, methoxycarbonamido, butoxycarbonamido) and acyloxy groups (for example, acetyloxy, propionyloxy, butyroyloxy).
A4 may further have a substituent which is exemplified above as in A4. It is preferable that the group represented by A4 (optionally substituted) has from 0 to about 36 carbon atoms.
Preferable examples of A4 include alkyl groups, aryl groups, heterocyclic groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, amino groups, carbonamido groups, ureido groups, urethane groups and halogen atoms. Among all, alkyl groups are particularly preferable therefor. n is an integer of from 0 to 4. When n is 2 or more, A4""s may be either the same or different from each other. When n is 2 or more, A4""s may be bonded together to form a ring. It is preferable that n is 0 or 1.
Examples of A5 and A6 include a hydrogen atom and the groups cited above as the examples of A4. Preferable examples of A5 and A6 include a hydrogen atom, alkyl groups, aryl groups, heterocyclic groups, acyl groups, sulfonyl groups, carbamoyl groups, alkyloxycarbonyl groups, aryloxycarbonyl groups, amino groups and alkyloxy groups. Among all, alkyl groups are particularly preferable. These groups may have further substituents. A4, A5 and A6 may be bonded together to form a ring.
Examples of A7 include a hydrogen atom and the groups cited above as the examples of A4. It is preferable that A7 is a group which adequately leaves as an Oxe2x95x90Cxe2x95x90Nxe2x80x94A7 molecule together with the coupler leaving group after the formation of a color developing agent precursor from a color developing agent and a coupler so as to form a dye. Examples of such a group include a hydrogen atom, alkyl groups, aryl groups, heterocyclic groups, sulfonyl groups, carbamoyl groups, alkyloxycarbonyl groups, aryloxycarbonyl groups, amino groups, alkyloxy groups and aryloxy groups. Among all, a hydrogen atom and alkyl, aryl and heterocyclic groups are preferable as A7.
A8 represents xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94N(A11)xe2x80x94 or xe2x80x94C(A12) (A13). A9 represents xe2x95x90O, xe2x95x90S, xe2x95x90Nxe2x80x94A14 or xe2x95x90C (A15)xe2x80x94C (A16)xe2x95x90Nxe2x80x94A17. Examples of A10 to A17 include the groups cited above as the examples of A4. It is favorable that the group formed by A8 to A10 and the carbon atom is a group which appropriately leaves from the color developing agent precursor represented by general formula (VI) under heating or the action of another compound to thereby form a color developing agent. Examples thereof include groups represented by the following general formulae (XIII) to (XVI): 
In general formulae (XIII) to (XVI) A32 to A40 are substituents while A41 is as defined in the illustration of A9. Preferable examples of A32 to A40 include alkyl groups, aryl groups, heterocyclic groups, sulfonyl groups, carbamoyl groups, alkyloxycarbonyl groups, aryloxycarbonyl groups, amino groups, alkyloxy groups and aryloxy groups. Among all, alkyl groups are particularly preferable therefor. Among the groups represented by general formulae (XIII) to (XVI), those of general formula (XIII) are particularly preferable.
Next, particular examples of the compounds represented by general formula (I) will be listed. However it is to be understood that the invention is not construed as being limited thereto. 
The compound represented by general formula (VI) according to the invention may be synthesized usually by two routes. Namely, one route (1) whereby the compound of general formula (VI) is synthesized starting from a color developing agent of general formula (VI-1) via a compound of general formula (VI-2); and the other route (2) whereby the compound of general formula (VI) is synthesized starting with a color developing agent of general formula (VI-1) via a compound of general formula (VI-3).
Route (1) 
Route (2) 
The compound of general formula (VI-2) can be synthesized from the color developing agent of general formula (VI-1) usually by reacting the color developing agent of general formula (VI-1) or its salt (for example, hydrochloride, sulfate) with Xxe2x80x94A25 (wherein X represents a leaving group such as a halogen atom, a phenoxy group or an acyloxy group) or an equivalent thereof (for example, isocyanate) The reaction solvent to be used therein may be appropriately selected from among publicly known solvents such as ethyl acetate, chloroform, methylene chloride, acetonitrile, isopropyl alcohol, tetrahydrofuran, toluene and N,N-dimethylacetamide. In this reaction, it is also possible, if needed, to use a base such as triethylamine, pyridine, ammonia, pyrrolidine, DBU, sodium hydride, t-butoxypotassium, potassium carbonate or aqueous solution of sodium hydrogencarbonate. When the compound represented by Xxe2x80x94A25 can be hardly obtained, it is also possible that a compound of general formula (VI-4) or general formula (VI-5) (wherein X presents a leaving group such as a halogen atom, a phenoxy group or an acyloxy group) is synthesized from the compound of general formula (VI) and then reacted with a compound represented by Xxe2x80x94A26 (in case of the compound of general formula (V-4)), or a compound represented by Xxe2x80x94A27 (in case of the compound of general formula (VI-5)) to thereby give the aimed compound of general formula (VI-2). 
The compound of general formula (VI) can be obtained by reacting the compound of general formula (VI-2) with Hxe2x80x94Sxe2x80x94A24 or itys salt (for example, ammonium salt, sodium salt) in the presence of an oxidizing agent. The reaction solvent to be used therein may be exemplified by those cited above. The oxidizing agent can be appropriately selected from publicly known oxidizing agents such as manganese dioxide, silver acetate, ammonium persulfate, potassium permanganate, iodine and N-chlorosuccinimide. In this reaction, it is also possible to use a base, if needed, examples of which are the same as cited above.
In the route (2) wherein the compound of general formula (VI) is synthesized starting with the color developing agent of general formula (VI-1) via the compound of general formula (VI-3), the color developing agent of general formula (VI-1) or its salt (for example, sulfate, hydrochloride) is reacted with Hxe2x80x94Sxe2x80x94A24 or its salt (for example, ammonium salt, sodium salt) in the presence of an oxidizing agent to give the compound of general formula (VI-3). The reaction solvent, the oxidizing agent and the coexisting base to be used therein are each exemplified by those described above.
The compound of general formula (VI) can be synthesized by reacting the compound of general formula (VI-3) with Xxe2x80x94A25(wherein X represents a leaving group such as a halogen atom, a phenoxy group or an acyloxy group) or an equivalent thereof (for example, isocyanate). The reaction solvent and the coexisting base to be used there in are each exemplified by those described above.
Once synthesized by such a method, the compound of general formula (VI) may be further modified to thereby give a compound of general formula (VI) which is more appropriate for the desired use. A21 to A27 employed in illustrating the production methods are the same in the meaning as A21 to A27 defined in illustrating general formula (VI).